Aromatic polyester textile fibers dyed with bis(arylamino) dihydroxyanthraquinone dyes

ABSTRACT

Aromatic polyester textile material is dyed with anthraquinone dyes made by the reaction of an arylamine, such as aniline, with a dichloro-dihydroxyanthraquinone in which one of the chlorine atoms is in a non-peri position, the reaction being conducted in the presence of an acid acceptor and a copper catalyst. This class of anthraquinone dyes, when appropriately dispersed, provides clear blue dyeings on aromatic polyester fabrics with excellent substantivity, very good sublimation fastness, and excellent fastness to light. The dyes are applied to polyesters, such as polyethylene terephthalate, by carrier, pressure and thermofixation methods.

United States Patent 1 Botros l l AROMATIC POLYESTER TEXTILE FIBERS DYED WITH BIS(ARYLAMINO) DIHYDROXYANTHRAQUINONE DYES [75] Inventor: Raouf Botros, Lock Haven, Pa.

[73] Assignee: American Aniline Products, Inc.,

Lock Haven, Pa.

221 Filed: May 17, 1972 21 App1.No.:253,995

Related US. Application Data [63] Continuation-impart of Ser. No. 222,361, Jan. 31,

[52} US. Cl 8/39, 260/377, 260/380 [51'] Int. Cl. D06p 3/54, C07c 97/14, C09b 1/50 [58] Field of Search..... 8/39 R, 39 C, 179; 260/377,

[56] References Cited UNITED STATES PATENTS 1,969,735 8/1934 Ellis et a1. 8/40 X 2,480,269 8/1949 Seymour et al 260/380 X OTHER PUBLICATIONS I Salvin et al., Relation of Dye Structure to Properties [451 Feb. 12, 1974 of Disperse Dyes, American Dyestuff Reporter, July Primary ExaminerDonald Levy Assistant ExuminerBruce H. Hess Attorney, Agent, or Firm-Armstrong & Wegner [57] ABSTRACT ethylene terephthalate, by carrier, pressure and ther mofixation methods.

5 Claims, No Drawings AROMATIC POLYESTER TEXTILE FIBERS DYED WITH BIS(ARYLAMINO) DII-IYDROXYANTHRAQUINONE DYES CROSS REFERENCE TO RELATED APPLICATIONS BACKGROUND OE THE INVENTION Among the polyester fibers, those based on polyethylene terephthalate continue to be the most important, although fibers based on 1,4-dimethylcyclohexane terephthalate have become commercially available. Developments in both homoand copolyesters have continued and many modified versions of polyethylene terephthalate have recently appeared on the market. With the advent of new fibers, the search has continued for dyes which build up on the various types of polyester fabric proportionate to the amount of dye applied, and which are characterized by good light and excellent sublimation properties.

In polyester fibers, the diffusion of the dye into the fiber is effectively controlled by the mobility of the chain molecules in the disordered regions. However, the molecular shape and the size of the dye, the presence of polar groups and general steric considerations are also important in relation to the rate of diffusion.

Bis(arylamino)dihydroxyanthraquinones are known as colors for cellulose acetate or organic derivatives of cellulose from the teachings of Seymour and Salvin, U.S. Pat. No. 2,480,269. In the dyes of Seymour and Salvin, both of the arylamino groups are in a periposition because the dyes are made by the replacement of the nitro groups of 4,5-dinitro chrysazin or 4,8- dinitro-anthrarufin. Ellis in U.S. Pat. No. 1,969,735 suggests that certain dyes made by the reaction of an aryl amine with a dichloroanthrarufin can be used or cellulose esters or ethers.

1 have discovered that certain bis(arylamino)dihydroxyanthraquinone dyes provide dyeings of a deep blue hue when applied to polyester textile material by conventional methods. Dyed fabric provided by the invention can be after-treated as required with excellent results.

SUMMARY OF THE INVENTION In accordance with the invention, there is provided aromatic polyester textile material dyed with a dye of the formula:

In the above formula, one X is H and the other, is OH; R is a member selected from the group consisting of hydrogen, chlorine, bromine, alkyl having from 1-8 carbon atoms, alkoxy having from l-8 carbon atoms, hy-

droxy lower alkyl, N-lower alkylamino, N,N-di lower alkylamino, lower alkoxy lower alkyl, lower alkoxy lower alkoxy andacylamido having up to 7 carbon atoms. The term lower designates an alkyl group having up to 6 carbon atoms. n has a value of l-3.

The dyes for use in the invention are made by admix ing a 4,z-dihalochrysazin or 4,y-dihaloanthrarufin in which 2 may be the 7-position and y may be the 6- position, an aryl amine of the formula DETAILED DESCRIPTION The starting material for making the dyes used in the invention is a dihalochrysazin or diahaloanthrarufin made by treating chrysazin or anthrarufin with sulfuryl chloride or bromine in nitrobenzene at reflux for several hours. The resulting product is a 4,2- dihalochrysazin or a 4,y-dihaloanthrarufin, in which Li 2 may be the 7-position and y may be the 6-position of the anthraquinone nucleus. The literature reports the dichlorination of chrysazin (1,8-dihydroxyanthraquinone) by treating it with chlorine in aqueous acetic acid at C; DRP 127,669 Frdl. 6 328. An alternate process is described in DR? 172,300, Frdl. 8 274, in which chrysazin is treated in aqueous sulfuric acid at with potassium chlorate and sodium chloride. The products of both processes are said to' be 4,5- dichlorochrysazin. However, according to the experimental results using my recommended halogenation procedure, one of the halogens is in a non-peri position. The dihalochrysazin or dihaloanthrarufin thus produced provides a unique product when treated accord-- ing to the method of the invention.

The dihalodihydroxyanthraquinone is allowed to react with at least a stoichiometric quantity of an aryl amine of the formula: V

Aryl amines which may be used to produce dyes of the invention include: aniline; o,m,p-toluidine; the various xylidines; o,m, and p-dichloroaniline; o,m, and panisidines and phenetidines; p-aminoacetanilide, N-methyI-p-phenylenediamine; N,N-dimethyl-pphenylenediamine; p-butylaniline;p-n-octylaniline; p-tbutylaniline; p-amylaniline; p-n-heptylaniline; Z-[p- (aminoanilino)]ethanol; 2-(p-aminophenyl)ethanol; 2(p-aminophenoxy) ethanol; p-(2-methoxyethoxy)ani- 3 line; p-aminopropionanilide; and X-(p-aminophenyl) -n-octanol.

The reaction is conducted in the presence of an alkaline acid-binding agent and a copper'salt. Particularly useful acid-binding agents include the alkali metal carbonates, bicarbonates and acetates. Sodium acetate is preferred. The efficiency of the reaction is improved by the presence of a catalytic amount of a copper catalyst, such as copper sulfate or copper acetate.

The reaction mixture is heated to an elevated temperature between 120 C and the reflux temperature of the reaction mixture, usually about 220 C. It is convenient to use an excess of the amine reactant as a reaction medium, although it is possible to use substantially stoichimetric amounts'of reactants in the presence of an inert solvent. After completion of the reaction, which generally takes between 4-24 hours, the product is separated and recovered by conventional methods.

A particularly convenient way to recover the product in a purified form is to dilute the reaction mixture with methanol or denatured alcohol in an amount of 100 to 300% based on the volume of the reaction mixture. In

this method of product recovery, the reaction mixture is first cooled, the alcohol is added and the mixture is reheated to reflux. It is then allowed to cool gradually to room temperature, filtered, and the product collected on the filter is washed again with alcohol and thereafter, oven-dried. When suitable, the alcohol solution of the reaction mixture may be filtered hot.

To prepare the product for application to the polyester substrates the product must be suitably dispersed. This may be done in any ofseveral well-known methods, milling as'in a ball-mill withdispersing agents such as lignin sulfonic acid materials, for'instance. The resultant aqueous dispersion can be dried, as in a sprayd ryer, or preserved and; used as a paste. Standardization to any desired lower strength can be done with inert colorless diluents such as inorganic salts for powders, or water for pastes. Other materials such as preservatives, foam-control agents, and wetting agents may be added as desired.

Dispersed pastes are made bywet milling the dye in conventional equipment in the presence of a dispersing agent, preferably sodium lignin sulfonate or sodium alkylnaphthalene sulfonate, Various othercommercially available dispersing agents, such'as sodium salts of carboxylated polyelectrolytes and the naphthalene sulfonates; e.g., the condensation products of sulfonated naphthalene and formaldehyde, such as sodium dinaphthylmethane disulfonate, are conveniently used. The oil disperse paste may be cut or standardized to a standard strength with water. The final color content of the finished paste averages from -40 percent by weight (pure color) active dye base.

Disperse powders are prepared by wet milling color in the presence of a dispersant, such as those mentioned hereabove, in equipment such as a ball mill, Werner-Pfleiderer mill or attritor. The dispersed material is oven or spray dried and micropulverized if necessary to provide the dispersed powder. The color is cut or standardized to a standard strength in a blender with a diluent, such as sodium sulfate or dextrin. A wetting agent, such as sodium cetyl sulfate or an alkylphenoxy polyethanol may be added to aid in wetting out the product when it. is placed in the dye bath. Disperse powders are usually cut or standardized to 2560 percent by weight color content (pure color).

The dye, when added to water with or without auxiliary agents, forms a near colloidal aqueous dispersion from which the aromatic polyester fiber or textile material is dyed in the conventional manner at 40-l00 C (l04-212 F) to give a colored fiber containing about 0.0l2 percent by weight dye color basis).-

Alternatively, dyeing may be accomplished without a carrier at'temperatures of l00l50 C under pressure. Also, the dye may be applied in patterns by conventional printing methods, if desired.

The dye can be also applied to the aromatic polyester fiber by thermofixation methods, such as the Thermosol process. This process, which involves padding the cloth with the diluted dye dispersion followed by drying and heating with dried hot air or heated contact rolls, is conveniently used for dyeing polyester fibers and blends containing these fibers. Fixation temperatures of 180-220 C (356 428 F) are used for 30 to 90 seconds. If the fabric contains cotton or viscose rayon, apart from synthetic fibers, there is little danger of damaging cellulosic portions, but if wool 'is present, the temperature must be kept within l80200 C and the time must be reduced to 30 seconds.

In order to' evaluate the effectiveness of a particular dyefor a given type of fiber, the dyed fiber is examined for substantivity of the color, light fastness of the color, and resistance of the color to sublimation and washing. Specific tests for the evaluation of these important properties are described in the examples that follow.

My invention is further illustrated by the following examples:

EXAMPLE I 4,z-Dichl orochrysazin Charged into a 1 liter 4-neck flask, equipped with EXAMPLE 2 Charged into a 500 ml. 4-neck flask, equipped with stirrer, thermometer and a condensate trap at tached to an air condenser,

g. aniline,

31 g. 4,z-dichlorochrysazin (0.1 mole) prepared as described in Example I, 20 g. anhydrous sodium acetate, and 0.5 g. cupric acetate.

The reaction mixture was heated at l55160 for 4 hours. The mass was stirred to 80 and was diluted with 250 ml. denatured alcohol.

The mixture was heated to reflux, after which it was allowed to cool to room temperature overnight. The mass was filtered and the cake was washed first with lOO ml. denatured'alcohol, then with hot water until washings were clear. The cake was sucked dry.

Yield: 65 g. (wet cake) 35 g. dry content Th. Yield: 42 g. (83%) The cake was not dried. Standardization A color content paste was made. Charged to a ballmill 64 g. wet cake 34 g. 100% color, 66 g. sodium ligninsulfonate (Lignosol PTA), and

210 g. water.

The mixture was milled' until dispersion test was satisfactory.

EXAMPLE 3 An aqueous dye bath containing 10% Marcron L (a commercially available phenolic dye carrier) and 1% monosodium phosphate as a buffering agent was prepared. Type 54 Dacron" polyester fabric was treated in a bath at 120 C for 10 minutes, the fabric-to-water dye bath ratio being 1 40. The disperse dye made as described in Example 2 was added in an amount sufficient to provide a bath containing 0.4% dye based on the weight of polyester fibers. Dyeing was continued for one hour at 205 F and the fabric was removed from -the bath, rinsed and dried. Sample dyeings were tested for sublimation according to standard AATCC Color Fastness to Dry Heat (sublimation) Test No. 117- I967T, Page 123 of the 1970 Technical Manual of the American Association of Textile Chemists and Colorists. Dyed fabric was placed between a sandwich of undyed "Dacron polyester fabric and heat was applied for 30 seconds. Sublimation tests were made at 350 F and 400 F on goods as described above. The dyeing was characterized by a clear blue hue. Sublimation tests showed very little transfer of color, even at 400 F.

Similar very good results were obtained when the dye was applied to the fabric by thermofixation methods and then tested for sublimation as described above.

The dyeings we're also treated for light fastness by subjecting them to carbon arcfading in accordance with AATCC, Color Fastness to Light, Carbon Arc Lamp, Continuous Light Test No. 1'6A-l964, as detailed on page 127 of the 1970 Technical Manual of the AATCC. The dyeings showed break at hours exposure, indicating excellent fastness to light.

EXAMPLE 4 where A is independently hydrogen or methyl group charged into a' 500 ml. 4-neck flask, equipped with stirrer, thermometer and a condensate trap attached to an air condenser, 60 g. p-toluidine, and 60 g. -'aniline.

The mixture was heated to 60C. Then there was added 31 g. 4,2-dichlorochrysazin (0.1 mole), prepared as described in Example 1, 20 g. anhydrous sodium acetate, and 0.5 g. cupric acetate.

The reaction mixture was heated at l55-l 60C for 5 hours. When the reaction mixture was worked up as indicated in Example 2, 36 g. of a dye having the above structure was obtained. When dispersed and applied to polyester fabric, as described in Example 3, the dyeing was characterized by a bright greenish blue hue of excellent sublimation and good light fastness. The dyeing was also characterized by retention of hue under different sources of artificial light.

EXAMPLE 5 charged into a 500 ml. 4-neck flask, equipped with stirrer, thermometer and a condensate trap attached to an air condenser 120 g. m-chloroaniline,

3] g. 4,z-dichlorochrysazin, prepared as described in Example 1,

20 g. anhydrous sodium acetate, and

0.5 g. cupric acetate.

The reaction mixture was heated at 170-l C for 17 hours.

When the reaction mixture was treated as described in Example 2, 37 g. ofa dye having the above structure was obtained. The dispersed dye has an excellent color value when applied to the polyester fabric specially by thermofixation methods. The dyeing was characterized by a reddish blue hue of excellent sublimation and excellent light fastness.

EXAMPLE 6 When 150 g. aniline in Example 2 was replaced by g. p-toluidine, 36 g. of a dye having the structure:

EXAMPLE 7 When 150 g. aniline in Example 2 was replaced by 120 g. p-anisidine, 34 g. of a dye'having the structure:

OH O OH was obtained. When dispersed and applied to polyester fabric as described in Example 3, the dyeing was characterized by a greenish blue hue of good light fastness and sublimation.

EXAMPLE 8 4y-Dichloroanthrarufin When 96 g. chrysazin in Example 1 was replaced by 96 g. anthrarufin, 85 g. 4,y-dichloroanthrarufin was obtained.

EXAMPLE 9 When 31. g 4,z-dichlorochrysazin in Example 2 was replaced by 31 g. 4,y-dichloroanthrarufin, 40 g. of a dye having the structure:

was obtained. When dispersed and applied to polyester pable of being formed into a shaped article, including semi-rigid materials which may be deformed by application of pressure.

As rigid plastic substrates of the invention may be mentioned terpolymers, including acrylonitrilestyrene-butadiene, often known as ABS; acrylics, including methacrylics; polystyrene, both foamed and rubber modified polysulfones; cellulosic derivatives, particularly esters such as cellulose acetate, propionate and butyrate; polyamides such as nylon; epoxy and phenolic resins; polycarbonates; and polyesters, It is understood that the rigid plastic substrates include those materials capable of being pigmented with the compounds of the invention, and therefore copolymers of the above classes of compounds, such as styrenebutadiene, are also within the scope of the invention.

Specific examples of thermoplastic resins include polyvinyl chloride, polyvinyl acetate, vinyl chloride- /acetate copolymers, polyvinyl alcohol, polyvinyl acetal, ethylene/vinyl acetate,-ethylene/vinyl propionate, ethylene/vinyl isobutyrate, ethylene/vinyl alcohol, ethylene/methyl acrylate, ethylene/ethyl acrylate ethylene/ethyl methacrylate, ethylene/ally] alcohol,

ethylene/ally] acetate, ethylene/ally] acetone, ethylene- /allyl benzene, ethylene/ally] ether, ethylene/acroleih, polyhexamethyiene adipamide, polyhexamethylene sebacamide, polycaprolactam, polymethyl methacrylate, polyacrylonitrile, polymethyl acrylate, polyethyl methacrylate, and styrene/methyl methacrylate.

As preferred rigid plastic substrates of the invention may be mentioned the polyacrylates, polystyrene and polycarbonates.

The rigid plastic substrates are colored with the compounds of the invention through pigmentation processes. The compounds are admixed with the plastic using sets of mixing rollers, mixing or milling apparatus. After the compounds and the plastic have been thoroughly mixed, the resultant colored mixture is shaped into the desired final form through procedures well known to those skilled in the art, such as pouring, calsubstrates of the invention include those materials caendering, extrusion, spreading, or injection molding. Where the desired product is a semi-rigid material, plasticizers may advantageously be added prior to shaping into the desired final form. As plasticizers suitable for this purpose may be mentioned esters of phthalic acid. Although the plasticizer may be incorporated after the mixing ofthe compound of the invention with the rigid plastic substrate, it also can be incorporated into the rigid plastic material prior to mixing the pigment with the rigid plastic material. In order to vary the strength of the finished product or vary the color, it is also possible to add additional pigments or fillers in an amount sufficient to obtain the desired effect.

The amount of the compound of the invention which is used to color the rigid plastic substrates may vary widely depending upon the degree of color wished to be imparted to the final product, and depending upon whether the compound of the invention is the sole colorant or whether it is used in admixture with other plastic colorants. When the compound of the invention weight in relation to the rigid plastic substrate. An

amount of colorant compound which has proved par ticularly valuable is about 0.000l% to about 1%.

EXAMPLE l Methylmethacrylate resin is covered with the com pound of Example 2 as the colorant, in a ratio of 2 grams resin to 1 mg. colorant. The resin is prepared by placing 1 pound of methylmethacrylate into a Thropp mill (a 2-roller mill), which is then heated and run in order to melt and smash the resin to a molten mass. The compound of Example 2 is added and the entire mixture of resin and colorant is milled until the colorant is uniformly distributed in the mass as measured by eye. While still hot, 30 grams of the hot mass is cut off for use in the following procedure. The sample, containing 30 grams methylmethacrylate and 15 mg. of the compound of Example 2 as colorant, may be conveniently molded in a Laboratory 40 Single Acting Watson- Stillman Laboratory Press (Farrell-Birmingham Co. 50-ton press). 30 grams of methylmethacrylate mixture containing 15 mg. of the compound of Example 2 per pound of methyl-methacrylate is placed in the cold mold, which is then closed with the Schrader Valve. The drain is opened and steam is applied to the mold. When steam comes through the drain pipe, the drain is closed. Up to 25.0 tons pressure is exerted on the chips until the mold is fully closed. This can conveniently be accomplished by observing the pressure gauge. When the gauge needle no longer decreases in pressure, th mold is then closed.

The mold is held closed at zero pressure by releasing the hydraulic pressure and maintaining the steam for five minutes. The mold pressure is increased to tons and held for ten minutes, the steam remaining on.

The mold pressure is increased to tons and the steam shut off; the drain is opened and cooling water is added for five minutes. Thereafter the pressure is changed to zero and the mold is opened to extract the resultant plastic chip.

EXAMPLE 11 EXAMPLE 1 2 The compounds of the invention may also be used as colorants for plastics made from polycarbonates. A pigmented plastic material of polycarbonates and the compound of Example 2 may be prepared according to the following procedure:

A specimen is prepared by dry mixing pelletized or powdered resin with finely divided colorant until uniform distribution is achieved of the colorant in the resin material. Plasticizer may also be added, if desired. The

mixture is then extruded or injected molded under suitcorresponding to Example 10 to produce a pigmented plastic material is fed into the injection molder, to produce pigmented chips having excellent fastness characteristics.

EXAMPLE 13 When the compounds of Examples 3-9 are substi tuted for the compound of Example 2 in the process of Example 10, methylmethacrylate is colored to produce a clear blue shaped plastic material. The compounds of Examples 3 9 may be used to impart coloration to polystyrene following the procedure of Example 1 l and polycarbonate is pigmented with the compounds of Examples 3-9 following the procedure of Example 12.

I claim:

l. Aromatic polyester textile fibers dyed with a dye of the formula: V

X (a (|)H I ll l6 l l sl (R) 5 H (R)n X 0 NH wherein one X is H and the other is OH; Ris a member selected from the group consisting of hydrogen, chlorine, bromine, alkyl having from l-8 carbon atoms, alkoxy having from l-8 carbon atoms, hydroxy lower alkyl, N'-lower alkylamino; N,N-di lower alkylamino, lower alkoxy lower alkyl, lower alkoxy lower alkoxy and acylamido having up to 7 carbon atoms; and n has a value of 1-3.

2. The dyed fibers of claim 1 wherein R is hydrogen,

a the X in the 8-position is OH and the other X is H.

3. The dyed fibers of claim 1 wherein R is methyl, n is 1, the X in the 8-position is OH and the other X is H.

4. The dyed fibers of claim 1 wherein one R is hydrogen, and the other R is p-methyl group, n is 1, the X in the 8-position is OH and the other X is H.

5. The dyed fibers of claim 1 wherein R is Cl, n is l,

the X in the 8-position is OH and the other X is H. 

2. The dyed fibers of claim 1 wherein R is hydrogen, the X in the 8-position is OH and the other X is H.
 3. The dyed fibers of claim 1 wherein R is methyl, n is 1, the X in the 8-position is OH and the other X is H.
 4. The dyed fibers of claim 1 wherein one R is hydrogen, and the other R is p-methyl group, n is 1, the X in the 8-position is OH and the other X is H.
 5. The dyed fibers of claim 1 wherein R is C1, n is 1, the X in the 8-position is OH and the other X is H. 